Anthraquinone vat dyestuffs of the phthaloylacridone series



United States Patent 3,164,593

koxy, carbalkoxy, acyl or alkylsulfonyl groups. It is ad- 3,164,593 vantageous to use compounds of the formula ANTHRAQUINONE VAT DYESTUFFS OF THE PHTHALOYLACRIDONE SERIES Eduard Moergeli, Muttenz, Switzerland, assignor to Ciba I 5 Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed May 20, 1963, Ser. No. 281,812 Claims priority, application Switzerland, May 28, 1962,

6 Claims. (Cl. 260249) 10 The present invention provides valuable blue anthraquinone vat dyestuffs of the formula in which X represents a chlorine atom or a trifluoromethyl (I) N group and n represents an integer not greater than 3. The

Patented Jan. 5, 1965' following may be mentioned by way of example: phenol, (|3 NH A l-hydroxy 3 trifluoromethylbenzene, 1-hydroXy-3 :S-di- N ll (trifluoromethyD-benZene and more especially l-hydroxyn 2- or 4-chlorobenzene, 1-hydroxy-2- or 4-methylbenzene,

I 1-hydroxy-3-methoxybenzene, l-hydroxy-Z- or 4-bromo- Q benzene, 4-hydroxybenzene carboxylic acid methyl ester or I I 2- or 4-hydroxyacetophenone. in which A represents a 3:4-phthaloylacridone residue The reiilchohs are advantageously Carried out in a 1- bound to the NH- group in 2-position and Rrepresents vent dlhlehtthe p ph of a p u of a benzene id the Formula 3, the condensation is advantageously car- The new dyestuff are obtained by condensing one mol fled h an 5 1 edlum in the cold, an inert solof cyanuric chloride in any desired sequence with 2 mols h mlsclble Wlth Water, for p acetone or dlOXane of 2-amino-3:4-phtha1oylacridone and one mol of a hybelhg advantageously t0 the Water, d fllso h droxybenzene. agent capable of binding acid, for example, sodium b1- Thus, one mole f cyanuric chloride can fi t be carbonate, sodium carbonate or sodium hydroxide. The densed with 2 mols of the 2-amino-3:4-phthaloylacridone of a comphllhd 0f the Formula 3 W h a and the resulting condensation product of the formula 2-am1110-3 i4'phthaloylacl'ldone, the Condensatloh 0f y uric chloride With a 2-amino-3:4-phthaloylacridone to form a compound of the Formula 2 and the condensation (2) of the latter compounds with the hydroxybenzene have to be carried out under much more rigorous conditions, the

l; l; A reactions advantageously being performed in a solvent having a high boiling point, for example, nitrobenzene,

| ortho-dichlorobenzene, naphthalene or phenol and their 01 derivatives. These reactions are advantageously carried out at a temperature above 100 C. To obtain a comthen condensed with a hydroxybenzene or, advantageouspound of Formula 2 the condensation is advantageously ly, one mol of cyanuric chloride is first condensed with carried out in nitrobenzene, and the subsequent stage is one mol of the hydroxybenzene to form the condensation advantageously carried out in an excess of the hydroxyproduct of the formula 331126116- The products obtained by the process of the invention (3) N are suitable for dyeing and printing a very wide variety of materials, especially for dyeing and printing fibres made of natural or regenerated cellulose. The dyeings obtained N therewith are distinguished by valuable reddish blue tints and by a good fastness to light. They have good propero I ties of wet fa'stness and are especially fast to soda boiling,

chlorine and chlorite. The new dyestuffs can also be used as pigments.

which is then condensed with 2 111015 of 23311110314 The following examples illustrate the invention. The phthaloylacridone to form the finished dyestuff. parts and percentages are by weight The 2-amino-3:4-phthaloylacridones used as starting materials in the process of the invention can contain sub- E l 1 stituents in the acridone or phthaloyl residue, for example, 7 halogen atoms. As examples unsubstituted 2-amino-3 :4- A mixture of 5.6 parts of 2-amino-7-chloro-3 :4-phthalophthaloylacridone may be mentioned and more especially ylacridone, 2.05 parts of 2-(2'-chlorophenoxy)-4:6-di- 2-amino-6- or -7-chloro-3:4phthaloylacridone. chloro-symmetrical-triazine, 0.3 part of metanitrobenzene The hydroxybenzenes used in the process of the invensulfonic acid and 50 parts by volume of nitrobenzene was tion can contain further substituents in the benzene residue, stirred for 16 hours at to C. and then for 3 hours for example, halogen atoms, or alkyl, trifluoromethyl, alat to C. 1 part by volume of benzoyl chloride hydrosulfite in 2000 parts of water.

was then added and the whole stirred for to 155 C. The dyestuff of the formula 3 hours at 150 which crystallized in the form of small blue needles, was filtered at 80 to 90 C., washed with nitrobenzene and alcohol and then dried. It dyed cotton blue tints fast to chlorite and soda boiling from a red-violet vat.

By replacing the 2-(2-chlorophenoxy)-4:6-dichlorosymmetrical-triazine by an equimolecular proportion of 2- 3 -trifluoromethyl-phenoxy) -4: 6-dichloro-symmetricaltriazine, 2- (4-chlorophenoxy) -4: 6-dichloro-symmetricaltria'zine and 2-phenoXy-4:6-dichloro-symmetrical -triazine, dyestuffs having similar dyeing properties were obtained.

By using 2-amino-6-chloro -3:4-phthaloylacridone or 2- amino-3:4-phthaloylacridone instead of 2-amino-7-chloro- 3'r4-phthal'0ylacridone and reacting with the aforemem tioned O chloro-phenoxy-dichloro-symmetrical-triazines as described above, products were obtained which gave reddish blue dyeings on cotton that likewise showed a high degree of fastness.

The phenoxy-4:6-dichlorotriazines were obtained, for example, as follows: with continuous stirring 'a solution of 18.4 parts of cyanuric chloride in 110 parts by volume of acetone was added dropwise at to C. to 200 parts by volume of water in the course of 10 minutes and then a solution of 16.2 parts of meta-trifluoromethylphenol in parts by volume of acetone was added dropwise at -5 to 0 C. in the course of 10 minutes. 8.4 parts of sodium bicarbonate were then quickly sprinkled into the mixture and the whole stirred until the cyanuric chloride disappeared. The resulting 2-(meta-trifinoromethylphenoxy) 4:6 dichloro symmetrical triazine was. filtered, washed with Water and dried in vacuo at to C. After recrystallization from ligroin (B1 to C.), the pure product melted at 96.5 to 98 C. (corrected). The following were obtained. in an analogous manner:

2 (2'-chlorophenoxy)-4:6-dichloro-symmetrical-triazine,

M.P. 96.5 to 975 C. (corrected), and

2 (4-chlorophenoxy)-4:6-dichloro-symmetrical-triazine,

MP. 111 to 112.5 C. (corrected).,

' Example 2 1 part of the dyestuff obtained as described in Example 1 was vatted at 50 C. in 100 parts of water with 2 parts of sodium hydrosulfite in the presence of 4 parts by volume of 30% sodium hydroxide solution. The stock vat so obtained was added to a solution of 6 parts by volume of 30% sodium hydroxide solution and 2 parts of sodium 100 parts of cotton were dyed for 1 hour at 50 C. in the dyebath so obtained in the presence of 20 parts of sodium chloride. The cotton was then squeezed, oxidized in the air, rinsed, acidified, rinsed again and then soaped at the boil. It was dyed a strong blue and the dyeing possessed very good properties of fastness.

What is claimed is: 1. An anthraquinone vat dyestuff of the formula in which X is a member. selected from the group consisting of chlorine and trifiuorornethyl, m is a whole number of at most 2 and n is a Whole number of at most 3.

2. The anthraquinone dyestuff of the formula 3. The anthraquinone dyestuff of the formula 4. The anthraquinone dyestuif of the formula 5. The anthraquinone dyestufi of the formula 6. The anthraquinone dyestufi of the formula References Cited in the file of this patent UNITED STATES PATENTS 1,568,627 Schetelig Jan. 5, 1926 1,663,474 Ackermann Mar. 20, 1928 1,719,792 Ackermann et a1 July 2, 1929 1,994,602 Wieners Mar. 19, 1935 2,567,821 Moergelic Sept. 11, 1951 2,716,645 Von Aug. 30, 1955 OTHER REFERENCES Venkataraman: The Chemistry of Synthetic Dyes, vols. I and II, Academic Press, Inc., N.Y., 1952, pp. 69, 348, 479, 916, 920, 925 ,and 1221.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,164,593 January 5, 1965 Eduard Moergeli It is hereby certified that] error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, lines 3 to 19, for the upper leftehand portion of the formula reading: a

read

same column 4, lines 60 to 75', for the lower center portion of the formula reading:

Signed and sealed this llth day of May 1965.

(SEAL) Attest:

ERNEST W. SW IDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 